Polysulphide copolymer



"Patented Nov 1944 UiE STATE-S :aPA'i E-NT j orsice 2,363,815 POLYSULPHH) E CGPOLYMEB Joseph Patrick, Morrisville, la., minor to Thiokol Corporation, Trenton, N. 1, storm)- ration of Delaware NoDrawing. Application June 6, 1940, Serial No. 339,075

8 Claims.

This invention relates to the production of polymerlc bodies-such as may be obtained by reacting an alkaline polysulphide with certain classes or organic compounds, and relates more particularly to the formation of copolymers.

Alkaline polysulphides can be reacted with organic compounds having'two adjacent carbon atoms to each of which is attached a substituent which is split ofi during the reaction, e. g., ethylene and propylene dihalides, this reaction being described in Patrick Patent 1,890,181. Certain typical polymers of this class, while possessing the advantage of relatively low cost of produc, tion, have the disadvantage that during the curing thereof'as such or in admixture with natural rubber, a disagreeable gas is evolved.

The disadvantage mentioned can be avoided and. other marked improvements effected if the space between the adjacent carbon atoms referred to is opened up and intervening structure placed therein, and polymeric products are thereby obtained which are substantially polymers of the unit Such polymers may be obtained by reacting an alkaline polysulphide with an organic compound having two carbon atoms joined to and separated by intervening structure to each of which carbon atoms there is attached a substituent which is split ofi during the reaction, as well as by other methods, as set forth, for example, in my era-pending application Serial No. 218,814, filed July 12, 1938, now United States Patent No. 2,2163%, issued September 24, 19i0. Theprice now paid forthis advantage is however, in gen- I eral, an increase in cost of production.

The two types of polymers described, that is.

those of the adjacent carbon atom type and those of the intervening structure type, may be copolymerized by various methods as, for example, as

set forth in my co-pending application Serial No. 267,389, filed April 12, 1939, and a cost advantage obtained. Unfortunately, however, certain typical representatives of these copolymers also possess the undesirable property or gas evolution previously mentioned. The adjacent carbon'atom type of polymer and copolymers made therefrom possess the characteristic structure -C.C.S8.C.CSS and the undesirable gas evolu- There is a tendency for and organic plastics.

duce a copolymer free from the disadvantageous gas evolution referred to. p

It is a further object to produce a copolymer which combines the marked advantages of the intervening structure" type of polymer with relatively low cost..

Other objects and advantages will hereinafter appear.

This invention is based, in part at least, on the discovery oi'the theory that the cause of the undesirable gas evolution from the'adjacent carbon atom type of polymer is the presence oi'the icecurring group this grouping to unidergo a cleavage, as shown by the dotted lines, withthe production of the obnoxious volatile compound H m-CH under reducing conditions which are present whether the compound is heated by itself or com... pounded with natural or other eynthetic rubbers The present invention is an application at the above mentioned discovery and constitutes one means of avoiding the above mentioned recur ring structure or unit, and by so doing I am en abled to obtain the desired absence of undesir able gas evolution in combination with high ual strength and-elasticity, etc.

B. Retention of these qualities over a. wide f range or temperature.v

- C. Freedom from undesirable gas evolution when worked.

tion appears to be traceable to this character- 1 isticstructure which, .it will be noted, is absent 1 irom the intervening structure type or polymer.

' It is an api a the'ipresent invention to pro- D. Low cost.- I The copolymers of this invention have the gen eral formula V l The symbols used in this'iormula have'alreldy where been defined. m and n are integers the ratio of which expresses the molecular ratio otthe radicals to which said integers are annexed.

It is to be noted that in this formula there is an absence of the grouping t l.Natasha,

1 Such copolymers mssesssubstantially all of the desirable properties of the intervening structure type polymer, including freedom from undesirable gas evolution. In addition they possess certain additional advantages including increased resistance to solvents in general, as well as an improved or decreased water absorption. Last.

Clccic A.Organic compounds in general having the formula represents carbon atoms joined to and separated by intervening structure and X and X represent substituents split ofi during the polysulphide reaction, in other words, organic compounds in generaihaving two carbon atoms separated by and r comprises reacting a substance which is substantially a polymer of the unit with a substance which is substantially a. polymer oftheunit The polymers can be separately made and reacted but are preferably made simultaneously or successively in the presence of each other and reacted with each other during the process. of formation because in this manner there is a reaction of the rmpective polymers in all possible degrees of polymerization and an intermingling of the reacted polymers in the resultant copolymeric entity.

, Various typical methods of fiecting the general reaction above described will be set forth below, it being understood that these are only illustrative.

1. Simultaneously react an alkaline polysulphide with a class A compound and a clam C compound.

2. React an alkaline polysulphide with a class 0 compound to form a polymer. Add more of the alkaline polysulphide, if necessary, and react 3. Proceed as in 2 but reverse the order, 1. e.,

first react a class A body with polysulphide to joined to intervening structure, each of said carhon :atoms jhaving joined thereto substituents split ofi during the polysulphide reaction.

These substances when reacted with an alkaline polysulphide produce polymers of the unit (:355 to a) Class B.Same as class A where X and X are 'SH groups. I

These 'substancm when suitably oxidized produce polymers of the unit. I

Class C..0rganic compounds in general having the formula R'/X HA where R is hydrogen or an alkyl, aryl or aralkyl group or radical. I

These substances when reacted with an alkaline polysulphide producesubstances which are polymersoitheunit i asent-producesubstances which are substantially lymers or the unit v (Ri el) In general, the process ot-the' present, invention C where Xand X are form a'first polymer, then a class C body to form a. second polymer and combinethe first and second polymers to form a copolymer.

4. Proceed as in 2 M3, but instead of adding additional polysulphide at the end of the first stage, employ, for the second stage, polysulphlde generated in the reaction. This may be done by adding a desulphurizing agent to the first formed polymer which will react-therewith and remove labile sulphur and simultaneously will be cork verted into polysulphide. Such desulphurlzing agent may, for example, be sodium monosulphide which as an incident of its desulphurizing action is converted into polysulphide.

5. Oxidize a class D body in alkaline solution to form a. first polymer, add to the-reaction mixture a class B body, oxidize this compound under alkaline conditions to form a second polymer preferably in the presence of the firstpolymer and react both polymers to form a copolymer.

All of these reactions are preferably carried out in dispersed condition in the presence of a suitable dispersion agent so as to obtain the products in the formof aqueous dispersions or latex-like liquids. The tremendous surface-of the polymer indispersed form facilitates interaction of the individual polymers to form copolymers.

The alkalin polysulphides in general may be used, that,is,--the di, tri, tetra, penta or hexa sulphides of, for example, the alkali or alkaline earth metals, ammonium and substituted ammo-r nium, and the rank orvalue of the sulphur in- I teger in the polymer wil1, in general, correspond I g to that in the alkaline polysulphide, and in this way copolymers may be directly produced-having the general formula when www.mw 1 tetra, pants or hexa sulphide, the formula of the resulting copolymer is Such polymers contain sulphur in labile condition which may he removed by treatment with a desulphurlzing agent, thus producing POLvmers which are wholly or partly in disulphide form as,

for example, polymers having the formula- Such a copolymer may be obtained not only by partly desulphurizing a polymer made by the polysulphide reaction, but also may be obtained directly by the oxidation of suitable dimercapto bodies, and the resulting polymer in disulphide form may then be treated with elementary sulphur to convert it into a polymer having the formula As a specific illustrative example the follow? ing will be given:

separately in a little water. The causticand the magnesium chloride solutions are separately added. to the polysulphide solution in the order named. The polysulphide mixture is contained in a suitable vessel or flask equipped with means for mechanical stirring and with a reflux condenser and thermometer. To. this mixture, while being agitated, are added 2 mols of methylene dichloride. slowly heated to a temperature of 140 F. and 2 mols of BB dichloro diethyl ether are then added at such a rate that about one hour is required for the complete addition of'the dichloro diethyl ether, and the temperature of the mix iscontrolled in such away that the heat of reaction does not result in temperatures greater than about 180 F. during the addition of the dichloro ether.

The reaction mix is then'heated' slowly to about 210-212 F. for about flfteenminutes to complete the reaction. The/reaction product, which is in the form of a rather finely divided latex, is then allowed to settle and the super- The mixture is then agitated and intermediate polymer, and such a curing process will be illustrated by the following example:

Exmu 2 Parts by weight 1. Polymer as above described 100. 2. Zinc oxide 5. 3. Benzothiazyl disulphide .025. 4. Stearic acid .05 5. Carbon black 50.

The .above components are thoroughly incorporated together as, for example, by working on rubber differential rolls, and the resulting compound is then subjected to curing by heating as,

for example, in a mold under hydraulically lmposed pressure to a temperature corresponding to about 40 pounds of steam or 287 F. for a period of about thirty minutes.

The curing greatly enhances and develops the inchoate physical properties of the intermediate potentially reactive polymer and produces a cured compound having mechanical and solvent resistance to a high degree. Instead of zinc oxide (2) Tensile strength pounds per sq. in" 1,800 Elongation per cent..- 400 Permanent set do 12 The material made in the abovemanner, when compounded and cured is not measurably swollen by a weeks immersion in ordinary motor gasoline, nor does it impart color to the gasoline, and

on a month's exposure to distilled water at a temperature of 120 F. the increase in weight due to water absorption is less than ,4 of 11%.

A unique characteristic of the type of copolymer' the pre, aration of which was given in Example 1, is that it may be mixed or combined in any proportion desired with natural rubber and the resuiting compound curedor vulcanized withopt the formation, even at the high temperature of vulcanization, of any irritating gas or odor, and

l the products derived from such a mixture can natant liquid is withdrawn, after which the latex may be washed or purified by successive changes of water with intervening settling and decantation.

The polymer in the latex is in an intermediate iormcapable of being cured by a subsequent curing or heat treatment. For example, the intermediate polymer may be coagulated from the latex by the addition of suflicient acid to render ess which develops the inchoate properties 01 the r swelling in solvents and high resistance to sun-V light and air oxidation are conferred on the rubber mixes.

The copolymer produced as above described has physical properties all-ofwhich are at least as good as the polymer made from BB dichloro ethyl ether by reaction with sodium polysulphide, and in some respects, particularly in re-' spect of water absorption, there is an improvement. 'On the other, hand, the cost of the oopolymer is substantially less than that oi" the polymer made from the ether derivative alone.

The approximate empirical formula of the above described uncured polymer This polymer may be treated with a desul-i phurizing :agent and converted into a polymer having the formula (cmsnm-wanommsn.

pro-

The desulphurization step will be illustrated as Y I I on. follows: 3 V X.GHi.0. OHe.(J.OHaGHaX'.

. I i Ha Proceed as in Example 1 and to the latex obtained as therein set forth, add -5 mols of NaOH 5 nmsmmmmhm' dissolved in about 300 cc. of water. ,The latex -l --B mixture, which-should be contained in a vessel i .Disubstituted dlpropyliormal fitted with mechanical agitation, is then stirred XICHICHIIOICEIOICH'ICHXI and is heated to about 200 F. for a period or mmpsflmm dmhymmal about thirty minutes. Under this treatment the I II I labile sulphur is removed from the organic com- X-CHIO.CH!.CH.OCHL pound by the caustic soda and a deep red polysulphide solution is formed by reaction of said labile sulphur with the sodium hydroxide desul- Dimbsflmm dimemoxyemm phurizing agent. The agitator is then stopp d. and the latex is allowed to settle out from the O liquid and thereafter a purified latex is obtained in the manner above described. Instead of alka- Disubstimgd pmdiemy line hydroxides or monosulphides, desulphurizing 2 x.CH20.CH!.cH!-oCH}-x'- 3 mmggneral ii inclgcdmg 0 Disubstltuted dimothoxy ethane y sulp es, sulp tes, drosu p es, e The polymer from which the labile sulphur has been removed in the above manner possesses, I Disubstituteddlproiiylihh ether upon curing, improved properties. For example, its tensile strength is higher; its resistanceto O O abrasion is very markedly increased; its resist- I ance to freezing is far greater than in the case of pr Disubstltuted p r other the untreated polymer. For example, where the untreated eopolymer would become still and may 1 O 2 even become brittle at'a temperature of about 5 below zero F., the copolymer treated as above Disubsflmted 81115018 described is still flexible at temperatures as low a 40 below zero F. The treated polymer is also C CH,.O.CH. X' much more resistant to permanent deformation as a result of pressure, that is to say, its resist- Disubstimled dibenzymh ance to cold flow is greatly increased as a consei x X quence of the removal of the labile sulphur. 0

The oopolymers obtained as in Examples 1 and 3 can also be obtained by numerous variations, 40 I some of which have been described above. For example, the copolymer in disulphide form can be obtained by oxidizing a mixture of dimercapto Dmubsmmgdiphenylemer methane and BB dimercapto ethyl ether in an 1 alkaline solution employing oxidizing agents in O F Q l general as, for example, air, oxygen, ozone, sodium hypochlorite, hydrogen peroxide, alkaline Disubetitute iire re idibenz iethe bichromates, manganates, permanganates and XCHLCHISOIICHICHLX,

- content of combined sulphur.

numerousother oxidizing agents, and the resulting polymer in disulphide form can then be f methyl treated with elementary sulphur, if it is desired x.cin.011i.critsotcnecntcnix' to convert it into a polymer havlnga higher Disubstimmd dmmpylsmphom Instead of dichlom ethyl hen the pres cntdcn.onto.cmcnto.cntcntdcntcnoom ent invention employs, in general, class A or class B compounds I Disubstituted dimethoxy tetra ethylene glyrol EXAMPLES or CLASS A AND CLASS B Comromms I CH CH CHAlCHJH CH Table L-lntervem'ng linkage characterized by I an ther inka e CH 05.x 0 0 11;}? SH I AA disubstituted propyl ether cmcmcm.momentum AA dixubstituted ethyl other x.c 114.0.0'H .x'. i a Gamma gamma disubstituted propyl other BB disubstituted ethyl ether I 55 CHs.CH.CHl-O.CHI-CH-CHI X.CH:.O.CH:-X'- ii I Disubstituted methyl ether I disubmmmd pmpyl ether x.c,ri.o.c,m.o.c,rii.xf. r cntcmcntoomcn cni Disubstituted ethoxy ethyl other I I I x.cini.s.cini.x'. I lu in beta disubstltuted propyl other Disubstituted thio ethyl other I (IJHLCHJ- Ha H- IL- KI X-CHl-S-CHz-X'. x

Diaubetitutedthiomethylethet I I u Alphen mddlmmituudmwlm oneomomommomomomc'm Alpha alphn dlmbetltnted butyl other omomcnomoomcmcmcm Beta beta dlsubstituted butyl ether c'ntcnomcm.momentum.cm-

Gamma gamma dlsubstituted hutyl other cmcmontcmocm.omemom' Delta delta dianbetitutod butyl other magmas male I!--Iutcrvening linkage characterized b unsaturated hydrocarbon structure Dlsubetltuted tolyl propane 2 x.om.qn=on.om.cm.x'

' Dlanbstituted pentone 2 XDHe-GH OHfiHmCHmCHmX' Dmuhatltntod hexcne 2 xcmcm.cn=cn.cm.cm.cm.x

1,7 dlsubetitutcd heptone 8f mom.om.cH=cE.cm.cm.x'

1,0 disnbatltuted hexane a mc.on=cn.cn.om

1,4 dlsubatltnted pentena 2 me.cmon cncmcacm 1,6 disubstltuted heptene 3 Table III-Interveniug structure characterized by saturated hydrocarbon structure x.cm.cm.on=.x' momwm) ...x'

(u may be 3 to or more) cn cmcmcmcflcm.on:

xomcmomx' X.CH9.CH.OHa-X' Table W -intervening structure characterized by aromatic structure x'om - m bmmm ortho xylene xomcncomemx' llp' Dimbstituted dlethyl benzene ea Diaubetltuted naphthalene omx" x on 1,; Dlmbltitutod meeityleno can? Dlmbetitnted, 1,4 dimothyl nephthnlene a Dlmbetltuted mam nuubmmud pare an hutyl benzene xnm'omcncmomomimcntcm Dlmbetltnted para hexyl propyl benzene tmflvfi or 01. C m Cues D Comomms 11 plea of these classes are listed below,

whennmexbo, forexample,1to30- .0m om c The above are examples of 3,1 disubstituted aliphatic saturated hydrocarbons 1,1 disubstituted propane 2 1,1 disubotitutad butane 2 C En Disubstituted alpha methyl naphthalene atom, with a substance which is substantially a aaoaere application Seri No. 168,522 (now abandoned), filedOctober 11, 1937, and copending application Ser. No. 267,389, filed April 12, 1939.

I claim: Q

1. The process which comprises reacting a subsfialrtice which is substantially a polymer of the (rim) where R is selected irom the group consisting of a hydrogen atom, an alkyl radical, an aralkyl radical and an aryl radical, and S is a sulphur polymer of, the unit lambrepresents two carbon atoms joined to and separated by intervening structure, and S is a sulphur where atom, to form a copolymer.

' where x and)! are substituents which are split on during the reaction, to forms. first polymer,

For'the polysulphide reaction, xand X are.

substituents split 01! during said reaction and'ior the mercaptan reaction X and x' are -SH groups, as already explained.

The invention claimed and described in this application is disclosed in application Ser. No.

109,875 (now abandoned) flled'November 7, 1936,

2. The process which comprises reacting an alkaline polysulphide with an organic body having the formula 11 x n-o I t x! where R is selected from the group consisting of a hydrogen atom, an alkyl radical, an aralkyl radical andan aromatic radical, and X and X are substituents split of! during the reaction, to

iorm a first polymer; reacting an alkaline poiysulphide with an organic compound having the iormula x-t tga-x" where t i. la i represents an organic compoundhaving two carbon atoms Joined to and separated by intervening structure and X and x' are substituents split off during the reaction. to form a second polymer, and reacting the first polymer with the second polymer to form a copolymer.

3. The process which comprises reacting a substance which is substantially a polymer of the unit 7 (-CHaSa to o) with a substance which is substantially a polymer of the unit 7 (-C2H4.O.C:H4.Ss w a) 4. The process which comprises reacting an alkaline polysuiphide with an organic body having the formula v reacting an alkaline polysulphide with an or ganic body having the formula where Xand x' are substituents which are split oil during the reaction. to form a second polymer,

second polymers to second polymer and reacting the first and second polymers to form a copolymer.

6. The process which comprises reacting an 7 alkaline polysulphide with a mixture of methyle'ne dichloride and BB dichlor ethyl ether,

7.- A high molecular weight copolymer which is substantially the reaction product of a polymer ntthe unit (imam) I -.witho-nolymer of the unit where R is selected from the group consisting of .-a hydrogen .atom, an alkyl radical, an aralkyl and i (L l l represents two carbon atoms separated by and joined to intervening structure.

8. A high molecular weight copolymer which is substantially the reaction product of a polymer -oi the unit 31. B: to a) with a'polymer of the unitwhere represents two carbonatoms joined to-and separated by intervening structure and S is a. sulphur atom.

T JOSEPH, C. PATRI CK.

radical and an aryl radical, S is a sulphur atom 

